Magneto-structural correlations in a family of ReIVCuII chains based on the hexachlororhenate(iv) metalloligand

Abstract

Six novel one-dimensional chloro-bridged Re^IVCu^II complexes of formula {[Cu(L)₄][ReCl₆]}_n, where L = imidazole (Imi, 1), 1-methylimidazole (Meim, 2), 1-vinylimidazole (Vim, 3), 1-butylimidazole (Buim, 4), 1-vinyl-1,2,4-triazole (Vtri, 5) and N,N′-dimethylformamide (DMF, 6) are characterised structurally, magnetically and theoretically. The structures exhibit significant differences in Cu–Cl bond lengths and Re–Cl–Cu bridging angles, resulting in large differences in the nature and magnitude of magnetic exchange interactions between the Re^IV and Cu^II ions. Theoretical calculations reveal the coupling to be primarily ferromagnetic, increasing in magnitude as the bridging angle becomes smaller and the bond lengths shorten.